CN102696141A - Method of producing a sulfide solid electrolyte material, sulfide solid electrolyte material, and lithium battery - Google Patents

Method of producing a sulfide solid electrolyte material, sulfide solid electrolyte material, and lithium battery Download PDF

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CN102696141A
CN102696141A CN2010800572674A CN201080057267A CN102696141A CN 102696141 A CN102696141 A CN 102696141A CN 2010800572674 A CN2010800572674 A CN 2010800572674A CN 201080057267 A CN201080057267 A CN 201080057267A CN 102696141 A CN102696141 A CN 102696141A
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solid electrolyte
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sulfide
electrolyte material
sulfide solid
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CN102696141B (en
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大友崇督
川本浩二
滨重规
加藤祐树
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Toyota Motor Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

A method of producing a sulfide solid electrolyte material includes: forming an intermediate having crosslinking sulfur but no Li2S, by vitrifying, in a first vitrification process, a starting material composition obtained by mixing Li2S and a sulfide of a group 14 or group 15 element such that a proportion of Li2S with respect to the sum total of the Li2S and the sulfide of a group 14 or group 15 element is smaller than a proportion of Li2S required for the sulfide solid electrolyte material to obtain an ortho composition; and eliminating the crosslinking sulfur by vitrifying, in a second vitrification process, an intermediate-containing composition resulting from mixing a bond cleaving compound, which cleaves a bond of the crosslinking sulfur, with the intermediate.

Description

Make method, sulfide solid electrolyte material and the lithium battery of sulfide solid electrolyte material
Technical field
The present invention relates to make the method for the sulfide solid electrolyte material that produces minute quantity hydrogen sulfide.
Background technology
In recent years, information relevant apparatus and communicator such as personal computer, video camera, mobile phone etc. have been followed through being intended to develop as the battery of the power supply in the aforementioned means rapid diffusion.Simultaneously, the height output that is used for motor vehicle and motor vehicle driven by mixed power is at the continuous Research on development theme of automotive field with high-capacity battery.At present, lithium battery is occupied an leading position in polytype battery owing to its high-energy-density.
At present commercial obtainable lithium battery uses the electrolyte solution that comprises flammable organic solvent.As a result, safety device that must temperature raises during battery be equipped with to suppress short circuit, and in order to prevent short circuit, also need make and material aspect improvement.In contrast to this; As through electrolyte solution being changed into the lithium battery of the all-solid-state battery of solid electrolyte layer; In battery, do not adopt flammable organic solvents, and help simpler safety device demonstrably, excellent aspect manufacturing cost and productivity ratio simultaneously.Sulfide solid electrolyte material is the conventional solid electrolyte material that in such solid electrolyte layer, adopts.
Sulfide solid electrolyte material is exported owing to its high lithium (Li) ionic conductivity can be used for realizing higher battery, and relevant technologies is being studied.For example, people such as Nobuya, " Mechano-chemical Synthesis of Lithium Ion Conducting Materials in the System Li 2O-Li 2S-P 2S 5", J.Jpn.Soc.Powder Metallurgy the 51st volume, No. 2,91-97 discloses a kind of nature of glass Li ion conductive material, wherein at 75Li 2S-25P 2S 5In partial L i 2S is by Li 2O replaces.In addition, people's such as R.Prasada Rao " Oxysulfide glasses xLi 2O-(1-x) (0.6Li 2S-0.4P 2S 5) ", Journal of Power Sources 159 (2006) 258-262 disclose a kind of by formula 40Li 2O-36Li 2S-24P 2S 5(in this was formed, material was at xLi 2O-(1-x) (60Li 2S-40P 2S 5) in satisfy x=40) nature of glass Li ionic conductor of representative, and it is through the mechanical lapping manufacturing.In two kinds of technology, in a single vitrifying process (mechanical lapping process), make the Li ionic conductor.
Sulfide solid electrolyte material is favourable aspect high Li ionic conductivity, but on the other hand, and problem is that they produce hydrogen sulfide with water (for example moisture, hereinafter is similar) contact the time.To this background, the inventor has been found that the amount of the hydrogen sulfide that is produced can be adjusted to ortho acid through the composition with sulfide solid electrolyte material and form and reduce.Term ortho acid composition typically refers to through the highest oxyacid of hydrauture in the oxyacid that obtains with the monoxide hydration.Yet, have Li 2In the sulfide solid electrolyte material of S, the ortho acid composition is meant the Li that is added with maximum in the sulfide 2The composition that the crystal of S is formed.At Li 2S-P 2S 5In the material, for example, Li 3PS 4Form corresponding to ortho acid, make in mole Li 2S: P 2S 5Obtain to have the sulfide solid electrolyte material that ortho acid is formed during=75: 25 mixed starting material.Although the sulfide solid electrolyte material with ortho acid composition is than not having the more a spot of hydrogen sulfide of sulfide solid electrolyte material generation that ortho acid is formed; But this sulfide solid electrolyte material still discharges a spot of hydrogen sulfide, and has observed the reduction of Li ionic conductivity.Therefore, in order to increase the stability of sulfide solid electrolyte material, must further reduce the generation of hydrogen sulfide.
Summary of the invention
The present invention provides a kind of method of making the sulfide solid electrolyte material that produces very small amount of hydrogen sulfide.
First aspect of the present invention relates to a kind of method of making sulfide solid electrolyte material, it is characterized in that comprising: in the first vitrifying process through the vitrifying of starting material composition being formed have crosslinked sulphur but do not have Li 2The intermediate of S, said starting material composition passes through Li 2The sulfide of S and the 14th family or the 15th family's element is mixed into and makes Li 2S is with respect to said Li 2The ratio of the summation of the said sulfide of S and the 14th family or the 15th family's element obtains ortho acid less than said sulfide solid electrolyte material and forms required Li 2The ratio of S and obtaining; With in the second vitrifying process through making the composition vitrifying that contains intermediate eliminate said crosslinked sulphur, the said composition that contains intermediate makes the bond fission compound and the said intermediate of the bond fission of said crosslinked sulphur obtain through mixing.
In above-mentioned configuration, remove Li from it 2The intermediate of S forms in said first consolidation step, and the crosslinked sulphur in said intermediate is removed in said second consolidation step.Owing to do not contain Li 2S and crosslinked sulphur are so can obtain sulfide solid electrolyte material.Can obtain to produce the sulfide solid electrolyte material of the high safety of very small amount of hydrogen sulfide thus.
In the manufacturing approach according to this aspect, the ratio that said bond fission compound mixes with said intermediate can be substantially free of the ratio of the sulfide solid electrolyte material of crosslinked sulphur for acquisition.This characteristic allows to suppress the generation by the hydrogen sulfide that reaction caused between said crosslinked sulphur and the water.
In the manufacturing approach according to this aspect, said bond fission compound can be Li 2O.Through above-mentioned characteristic, at Li 2Oxygen among the O (O) element can be with the good efficiency crosslinked sulphur in the said intermediate that ruptures.In addition, do not produce hydrogen sulfide, even have the Li of unreacted excessive interpolation 2Also be like this during O.
In the manufacturing approach according to this aspect, the said sulfide of said the 14th family or the 15th family's element can be P 2S 5And in said starting material composition, in mole, said Li 2S is with respect to said Li 2S and said P 2S 5The ratio of summation can be less than 75%.
In manufacturing approach according to this aspect, in the said composition that contains intermediate, in mole, said Li 2S and said Li 2The summation of O is with respect to said Li 2S, said P 2S 5With said Li 2The ratio of the summation of O can be not less than 75%.Above-mentioned characteristic allows to obtain to be substantially free of the sulfide solid electrolyte material of crosslinked sulphur.
In the manufacturing approach according to this aspect, the said sulfide of said the 14th family or the 15th family's element can be GeS 2And in said starting material composition, in mole, said Li 2S is with respect to said Li 2S and said GeS 2The ratio of summation can be less than 66.7%.
In manufacturing approach according to this aspect, in mole, said Li 2S and said Li 2The summation of O is with respect to said Li 2S, said GeS 2With said Li 2The ratio of the summation of O can be not less than 66.7%.Above-mentioned characteristic allows to obtain to be substantially free of the sulfide solid electrolyte material of crosslinked sulphur.
In the manufacturing approach according to this aspect, the said sulfide of said the 14th family or the 15th family's element can be SiS 2And in said starting material composition, in mole, said Li 2S is with respect to said Li 2S and said SiS 2The ratio of summation can be less than 66.7%.
In manufacturing approach according to this aspect, in the said composition that contains intermediate, in mole, said Li 2S and said Li 2The summation of O is with respect to said Li 2S, said SiS 2With said Li 2The ratio of the summation of O can be not less than 66.7%.Above-mentioned characteristic allows to obtain to be substantially free of the sulfide solid electrolyte material of crosslinked sulphur.
In the manufacturing approach according to this aspect, the said first vitrifying process can be mechanical lapping.Above-mentioned characteristic makes it possible to process at normal temperatures and allows to make manufacture process to oversimplify.
In the manufacturing approach according to this aspect, the said second vitrifying process can be mechanical lapping.Above-mentioned characteristic makes it possible to process at normal temperatures and allows to make manufacture process to oversimplify.
Second aspect of the present invention relates to a kind of sulfide solid electrolyte material, and it comprises Li, the 14th family or the 15th family's element, O and S; And said material is substantially free of crosslinked sulphur, wherein Li 2The content of S is not more than 1 mole of %.
In above-mentioned configuration, Li 2S content is low.The result can obtain to produce the sulfide solid electrolyte material of very small amount of hydrogen sulfide.
In the sulfide solid electrolyte material according to this aspect, the 14th family or the 15th family's element can be P, and can be through making Li according to the sulfide solid electrolyte material of this aspect 2S, P 2S 5And Li 2The O vitrifying is made.
In sulfide solid electrolyte material according to this aspect, Li 2O forms phase.This characteristic allows to obtain to have even the sulfide solid electrolyte material of higher Li ionic conductivity.
The third aspect of the invention relates to a kind of lithium battery, and it has the active positive electrode material layer that comprises active positive electrode material; The negative electrode active material layer that comprises negative electrode active material; And be formed on the dielectric substrate between said active positive electrode material layer and the said negative electrode active material layer.In said lithium battery; One of at least comprise sulfide solid electrolyte material in said active positive electrode material layer, said negative electrode active material layer and the said dielectric substrate; Said sulfide solid electrolyte material comprises Li, the 14th family or the 15th family's element, O and S; And be substantially free of crosslinked sulphur, and have the Li that is not more than 1 mole of % 2S content.
Through using above-mentioned sulfide solid electrolyte material, above-mentioned configuration allows to obtain to produce the lithium battery of very small amount of hydrogen sulfide.
Therefore, the present invention allows to obtain to produce the sulfide solid electrolyte material of very small amount of hydrogen sulfide.
Description of drawings
With reference to accompanying drawing, from the explanation of following exemplary, aforementioned and other purposes, feature and advantage of the present invention will become obviously, and similar Reference numeral is used to represent similar key element in the accompanying drawing, wherein:
Fig. 1 is the flow chart of an instance that the method for manufacturing sulfide solid electrolyte material according to an embodiment of the invention is shown;
Fig. 2 A and 2B are used to explain according to the method for the manufacturing sulfide solid electrolyte material of correlation technique with according to the indicative figure of the method for the manufacturing sulfide solid electrolyte material of one embodiment of the invention;
Fig. 3 is the schematic cross section that an instance of the generating element in lithium battery according to an embodiment of the invention is shown;
Fig. 4 shows the measurement result of the amount of the hydrogen sulfide that is produced by the sulfide solid electrolyte material that in embodiment 1-3, obtains;
Fig. 5 shows the measurement result of the amount of the hydrogen sulfide that is produced by the sulfide solid electrolyte material that in Comparative Examples 1-4, obtains;
Fig. 6 is presented at the measurement result of the X-ray diffraction of the sulfide solid electrolyte material that obtains among the embodiment 1-4;
Fig. 7 is presented at the measurement result of the X-ray diffraction of the sulfide solid electrolyte material that obtains among the Comparative Examples 1-3;
Fig. 8 is presented at the measurement result of the X-ray diffraction of the sulfide solid electrolyte material that obtains in the Comparative Examples 4;
Fig. 9 is presented at the measurement result of the Li ionic conductivity of the sulfide solid electrolyte material that obtains among embodiment 1-3 and the Comparative Examples 1-4;
Figure 10 is presented at the measurement result of the x-ray photoelectron spectroscopy of the sulfide solid electrolyte material that obtains in the Comparative Examples 1;
Figure 11 is presented at the measurement result of the x-ray photoelectron spectroscopy of the sulfide solid electrolyte material that obtains in the Comparative Examples 2;
Figure 12 is presented at the measurement result of the x-ray photoelectron spectroscopy of the sulfide solid electrolyte material that obtains in the Comparative Examples 3; With
Figure 13 is presented at the measurement result of the x-ray photoelectron spectroscopy of the sulfide solid electrolyte material that obtains in the Comparative Examples 4.
Embodiment
Because to the painstaking research that addresses the above problem, the inventor finds to have sulfide solid electrolyte material that ortho acid forms, and to produce the reason of a small amount of hydrogen sulfide following.Particularly, the inventor finds, therein based on the mole meter with Li 2S: P 2S 5Can be under the situation of=75: 25 mixed starting material at Li 2S-P 2S 5Material in obtain ortho acid and form, but work as Li 2When the ratio of S is hanged down, or even hang down a bit, also can form a spot of S 3P-S-PS 3Unit (P 2S 7The unit), and the reaction of the crosslinked sulphur in said unit and water produce hydrogen sulfide.On the contrary, work as Li 2When the ratio of S is high, or even height a bit, also can remain a spot of Li 2S, itself and water reaction produce hydrogen sulfide.Therefore, the inventor finds that with regard to the sulfide solid electrolyte material that obtains the very small amount of hydrogen sulfide of generation, the composition of regulating starting material is very difficult.
The inventor also finds following content.At Li 2S-P 2S 5Be difficult to realize forming fully uniformly of nature of glass sulfide solid electrolyte material in the material, in addition with starting material form be adjusted to desired proportions (in mole, Li 2S: P 2S 5=75: also be like this afterwards 25).Therefore, a spot of above-mentioned Li 2S and crosslinked sulphur keep, and can produce hydrogen sulfide with the water reaction.The inventor also finds, even after the starting material composition is adjusted to desired proportions, also can produces about 10% and have the Li that non-stoichiometric is formed 4P 2S 6The unit, it can cause remaining Li 2The existence of S.
About correlation technique, the inventor finds, the manufacturing through the sulfide solid electrolyte material that will in a single glass process, implement is divided into two stages and can obtains to produce very small amount of hydrogen sulfide and not contain Li 2The sulfide solid electrolyte material of S and crosslinked sulphur saidly is divided into two stages and makes in the first vitrifying process, because Li 2S is eliminated fully (makes Li 2S introduces in the structure of intermediate fully), possibly have the intermediate of crosslinked sulphur and in the second vitrifying process, add the compound that is used to make crosslinked sulfide linkage fracture to intermediate, so produce to remove crosslinked sulphur thus.
Next be to illustrated in detail according to method, sulfide solid electrolyte material and the lithium battery of the manufacturing sulfide solid electrolyte material of one embodiment of the invention.Term ortho acid composition typically refers to the highest oxyacid of hydrauture in the oxyacid that obtains through the hydration with monoxide.Yet, at the Li that has according to this embodiment 2In the sulfide solid electrolyte material of S, the ortho acid composition is meant the Li that is added with maximum in the sulfide 2The composition that the crystal of S is formed.At Li 2S-P 2S 5In the material, for example, Li 3PS 4Form corresponding to ortho acid, make in mole Li 2S: P 2S 5Obtain to have the sulfide solid electrolyte material that ortho acid is formed during=75: 25 mixed starting material.
With the method for at first explaining the sulfide solid electrolyte material of making one embodiment of the invention.Method according to the manufacturing sulfide solid electrolyte material of this embodiment is characterised in that to have first consolidation step and second consolidation step, and but said first consolidation step forms the vitrifying of starting material composition, result to have crosslinked sulphur through the first vitrifying process do not have Li 2The intermediate of S, said starting material composition passes through Li 2The sulfide of S and the 14th family or the 15th family's element is mixed into and makes Li 2S is with respect to said Li 2The ratio of the summation of the said sulfide of S and said the 14th family or the 15th family's element is formed required Li less than obtaining ortho acid 2The ratio of S and obtaining; Said second consolidation step is eliminated said crosslinked sulphur through making the composition vitrifying that contains intermediate, and the said composition that contains intermediate makes the bond fission compound and the said intermediate of the bond fission of said crosslinked sulphur obtain through mixing.
In this embodiment, remove Li from it 2The intermediate of S forms in first consolidation step, and the crosslinked sulphur in intermediate is removed in second consolidation step.Owing to do not contain Li 2S and crosslinked sulphur the two, so can obtain sulfide solid electrolyte material.Thus, can obtain to produce the sulfide solid electrolyte material of the high safety of very small amount of hydrogen sulfide.Like what in about the correlation technique part, point out; When making sulfide solid electrolyte material with the single glass process; As stated, regulate starting material and form very difficulty, and exist about causing the quantitative limitation of the low hydrogen sulfide that is produced of which kind of degree.In contrast to this, this embodiment is through being divided into the vitrifying process sulfide solid electrolyte material that two stages allow easily to obtain to produce very small amount of hydrogen sulfide.
Fig. 1 is the flow chart that illustrates according to an instance of the method for the manufacturing sulfide solid electrolyte material of this embodiment.In Fig. 1, at first prepared Li 2S and P 2S 5(element of the 14th family or the 15th family).Then aforementioned substances is mixed to Li 2S: P 2S 5=70: 30 ratio (based on the mole meter) is to produce the starting material composition.Li 2S is with respect to Li 2S and P 2S 5The ratio of summation less than obtaining the ratio (75%) that ortho acid is formed.Next, make starting material composition vitrifying (the first vitrifying process), to produce 70Li through mechanical lapping 2S30P 2S 5Glass (intermediate).As mentioned below, but said intermediate has crosslinked sulphur does not have Li 2S.Next, with 70Li 2S30P 2S 5Glass and Li 2O (bond fission compound) mixes, and comprises the composition of intermediate with generation.Next, make the composition vitrifying (the second vitrifying process) that comprises intermediate, to produce sulfide solid electrolyte material through mechanical lapping.
" Mechano-chemical Synthesis of Lithium Ion Conducting Materials in the System Li the above people such as Nobuya Machida that quote 2O-Li 2S-P 2S 5", J.Jpn.Soc.Powder Metallurgy the 51st volume, No. 2, people's such as 91-97 and R.Prasada Rao " Oxysulfide glasses xLi 2O-(1-x) (0.6Li 2S-0.4P 2S 5) ", among Journal of Power Sources 159 (2006) 258-262, utilize Li 2S, P 2S 5And Li 2The mixture of O is made sulfide solid electrolyte material through single mechanical lapping.In this case, as shown in fig. 2A, at Li 2S and P 2S 5Li in the time of reaction 2O and P 2S 5Reaction.As a result, there is a small amount of Li 2S is retained in the height possibility that can produce a small amount of hydrogen sulfide in the gained sulfide solid electrolyte material and thus, like what in following Comparative Examples, describe.In contrast to this, in this embodiment, at first through making Li 2S and P 2S 5Reaction produces Li 2SP 2S 5Glass is as shown in Fig. 2 B.At this moment, regulate Li 2S and P 2S 5Between ratio so that Li 2The S complete obiteration (makes Li 2S is introduced in the structure of intermediate fully).As a result, generation can have crosslinked sulphur (for example, following P 2S 7The unit) Li 2SP 2S 5Glass.After this, make Li 2SP 2S 5Crosslinked sulphur and Li in the glass 2The O reaction.As a result, can obtain not contain Li 2The sulfide solid electrolyte material of S and crosslinked sulphur, the amount of the feasible hydrogen sulfide that is produced can remain very little.
As crosslinked sulphur (for example, the P in intermediate 2S 7The unit) by bond fission compound (for example, Li 2The reaction equation that is taken place when O) rupturing provides as an instance following.Point out P like following reaction equation 2S 7Crosslinked sulphur S and Li in the unit 2The O reaction is to form PS 3OLi unit and PS 4The Li unit, crosslinked thus sulphur disappears.Although in following reaction equation, do not illustrate, the singly-bound S in each unit is S -, it has Li +Counter ion.
Formula 1
Figure BDA00001771997100081
To progressively explain the method for the sulfide solid electrolyte material of an embodiment making this embodiment below.In this embodiment, following step is all implemented in inert atmosphere (for example, Ar gas atmosphere) usually.
But first consolidation step in this embodiment is the vitrifying of starting material composition, result to be formed have crosslinked sulphur through the first vitrifying process do not have Li 2The step of the intermediate of S, said starting material composition passes through Li 2The sulfide of S and the 14th family or the 15th family's element is mixed into and makes Li 2S is with respect to said Li 2S adds the ratio of summation of said sulfide of the above the 14th family or the 15th family's element less than obtaining the Li that ortho acid is formed 2The ratio of S and obtaining.
In this embodiment, Li 2S is eliminated in first consolidation step fully (makes Li 2S is introduced in the structure of intermediate fully), the result produces the intermediate that can have crosslinked sulphur.Like what in this embodiment, use, term " crosslinked sulphur " is meant and is deriving from Li 2Crosslinked sulphur in the compound of the sulfide reaction of S and the 14th family or the 15th family's element.For example, through making Li 2S and P 2S 5The S that reaction obtains 3P-S-PS 3Crosslinked sulphur in the unit is exactly a case in point.Crosslinked sulphur like this tends to be easy to generate hydrogen sulfide with water reaction and result.Characteristic " has crosslinked sulphur " and can confirm based on the measurement of raman spectroscopy spectrum.For example, at Li 2S-P 2S 5Under the situation of the sulfide solid electrolyte material of material, S 3P-S-PS 3The peak of unit appears at 402cm usually -1The place.Correspondingly, the existence of crosslinked sulphur or do not exist and to confirm based on this peak.Except Li 2S-P 2S 5In the sulfide solid electrolyte material outside the material, the existence of crosslinked sulphur or do not exist and can have the unit of crosslinked sulphur and confirm through identification through the peak of measuring these unit.
Next explain the starting material composition of this embodiment.The starting material composition of this embodiment is Li 2The mixture of the sulfide of S and the 14th family or the 15th family's element.Preferably, the Li in the starting material composition 2S can almost not have impurity, because side reaction in this case can be suppressed.Li 2The instance of S synthetic method is for example disclosing among the Japanese Unexamined Patent Publication No 7-330312 (JP-A-7-330312).Preferably, Li 2S can carry out purifying according to the method for describing among the WO 2005/040039 for example.
The starting material composition has the sulfide of the 14th family or the 15th family's element.The 14th family or the 15th family's element are not done concrete restriction, but for example can be P, Si, Ge, As, Sb etc.In aforementioned substances, preferably, the 14th family or the 15th family's element can be P, Si or Ge, particularly P, and this is because the sulfide solid electrolyte material that can obtain to produce a small amount of hydrogen sulfide and have high Li ionic conductivity in this case.The sulfide of the 14th family or the 15th family's element specifically can be P 2S 3, P 2S 5, SiS 2, GeS 2, As 2S 3Or Sb 2S 3
In this embodiment, have crosslinked sulphur but do not have Li in order to produce 2The intermediate of S is regulated the ratio in the starting material composition.Particularly, with Li 2S is with respect to Li 2The ratio of the summation of the sulfide of S and the 14th family or the 15th family's element is adjusted to less than obtaining the Li that ortho acid is formed 2The ratio of S.Sulfide at the 14th family or the 15th family's element is for example P 2S 5Situation under, obtain the Li that ortho acid is formed 2The ratio of S is 75% (Li 2S: P 2S 5=75: 25, based on the mole meter).Correspondingly, based on the mole meter, with Li 2S is with respect to Li 2S and P 2S 5The ratio of summation be adjusted to less than 75%.In this embodiment, can keep some Li 2S, even count above-mentioned Li based on mole 2The S ratio be 75% o'clock also be like this.This is because being difficult to obtain the perfect of nature of glass sulfide solid electrolyte material evenly forms, even the ratio in the starting material composition is being adjusted to desired proportions (Li 2S: P 2S 5=75: 25, based on the mole meter) time also be so, and have a small amount of Li 2S is retained in the chance in the material.In this embodiment, preferably, based on mole meter, Li 2S is with respect to Li 2S and P 2S 5The ratio of summation can be set at and be not more than 74%, more preferably no more than 73%, and especially, be not more than 72%, this is not have Li because can produce more reliably in this case 2The intermediate of S.
If the sulfide of the 14th family or the 15th family's element is GeS 2, then obtain the Li that ortho acid is formed 2The ratio of S is 66.7% (Li 2S: GeS 2=66.7: 33.3, based on the mole meter).Correspondingly, based on mole meter, Li 2S is with respect to Li 2S and GeS 2The ratio of summation be adjusted to less than 66.7%.In this embodiment, preferably, based on mole meter, Li 2S is with respect to Li 2S and GeS 2The ratio of summation can be set at and be not more than 66%, more preferably no more than 65%, and especially, be not more than 64%, this is not have Li because can produce more reliably in this case 2The intermediate of S.If the sulfide of the 14th family or the 15th family's element is SiS 2, then obtain the Li that ortho acid is formed 2The ratio of S is 66.7% (Li 2S: SiS 2=66.7: 33.3, based on the mole meter).Preferred Li 2The ratio of S can with GeS 2Situation identical.
In this embodiment, Li 2S is with respect to Li 2The ratio of the summation of the sulfide of S and the 14th family or the 15th family's element preferably can be not less than and obtain the burnt Li that forms 2The S ratio.This is because as above-mentioned Li 2The ratio of S is less than obtaining the burnt Li that forms 2During the S ratio, be not easy to form the MS that promotes ionic conductivity x(M represents the 14th family or the 15th family's element).At this, term Jiao is often referred to the high oxyacid of in through the oxyacid that obtains with monoxide hydration hydrauture second.Yet, utilizing Li 2In the sulfide solid electrolyte material of S, be meant in sulfide, to have the Li that is added with second maximum burnt the composition 2The composition that the crystal of S is formed.The burnt dehydrating condensation that also can be defined as through the ortho acid composition of forming is removed a structure that hydrone obtained from the ortho acid composition.For example, at Li 2S-P 2S 5In the material, Li 4P 2S 7Form corresponding to Jiao, make based on the mole meter with Li 2S: P 2S 5Obtain the burnt sulfide solid electrolyte material of forming during=66.7: 33.3 mixed starting material.Therefore, based on mole meter, Li 2S is with respect to Li 2S and P 2S 5The ratio of summation can preferably be not less than 66.7%, more preferably be not less than 67%, and be not less than 68% especially.
GeS therein 2Be under the situation of sulfide of the 14th family or the 15th family's element, obtain the burnt Li that forms 2The S ratio is 60% (Li 2S: GeS 2=60: 40, based on the mole meter).Therefore, based on mole meter, Li 2S is with respect to Li 2S and GeS 2The ratio of summation can preferably be not less than 61%, more preferably be not less than 62%, and be not less than 63% especially.SiS therein 2Be under the situation of sulfide of the 14th family or the 15th family's element, obtain the burnt Li that forms 2The S ratio is 60% (Li 2S: SiS 2=60: 40, based on the mole meter).Preferred Li 2The S ratio can with GeS 2Situation identical.
To explain the first vitrifying process below according to this embodiment.The first vitrifying process of this embodiment is to make that above-mentioned starting material composition is decrystallized to have crosslinked sulphur but do not have Li with formation 2The process of the intermediate of S.The instance of the first vitrifying process comprises for example mechanical lapping and melt quenching.Preferably, the first vitrifying process can be the mechanical lapping in the aforementioned process, and this is because mechanical lapping can be carried out at normal temperatures, and allows to make manufacture process to oversimplify.
Concrete restriction is not done in mechanical lapping, as long as the starting material composition is mixed and gives its mechanical energy simultaneously.Embodiment comprises for example ball milling, turbine mill, machinery fusion, mill.Preferably, mechanical lapping can relate to ball milling, relates to planetary type ball-milling especially, and this is because can obtain the intermediate of expectation in this case with good efficiency.
The mechanical lapping condition enactment is for being used for obtaining to have crosslinked sulphur but there is not Li 2The intermediate of S.If make intermediate, for example, in starting material composition and abrading-ball tank filling, and grind preset time with predetermined rotating speed through planetary type ball-milling.Usually, bigger rotating speed changes into intermediate generating rate faster.Equally, the processing time is long more, and then the starting material composition conversion ratio that changes into intermediate becomes high more.Speed setting in planetary type ball-milling for for example 200rpm (rpm) to 500rpm.In this scope, preferably, rotating speed can be 250rpm to 400rpm.Processing time in planetary type ball-milling for example is 1 hour to 100 hours.In this scope, preferably, the processing time can be 1 hour to 50 hours.
Next will explain the second vitrifying process according to this embodiment.This step is to make the composition vitrifying that contains intermediate eliminate the step of said crosslinked sulphur through the second vitrifying process, and the said composition that contains intermediate makes the bond fission compound and the said intermediate of the bond fission of said crosslinked sulphur obtain through mixing.
The composition that contains intermediate of this embodiment is the mixture of the bond fission compound of intermediate that in first consolidation step, obtains and the bond fission that makes crosslinked sulphur in the said intermediate.The bond fission compound is not done concrete restriction, and can for the alkali compounds of crosslinked reaction of Salmon-Saxl, for example Li 2O, Li 2O 2, Li 3N, Na 2O, K 2O, MgO or CaO.Preferably, the bond fission compound can be Li 2O, this is because Li 2Oxygen among the O (O) element can make the crosslinked sulphur fracture in the intermediate with good efficiency.In addition, Li 2O has the Li element, and therefore can strengthen the Li ionic conductivity of the sulfide solid electrolyte material that obtains through crosslinked sulphur fracture.
The amount of the bond fission compound that in second consolidation step, adds is not done concrete restriction, but preferably, can select rightly according to the reflecting point of for example bond fission compound.In this embodiment; Preferably; The bond fission compound can add with the ratio that allows acquisition to be substantially free of the sulfide solid electrolyte material of crosslinked sulphur, and this is because the generation of the hydrogen sulfide that can suppress in this case to cause because of the reaction between crosslinked sulphur and the water.Characteristic " is substantially free of crosslinked sulphur " and can confirms based on the measurement of raman spectroscopy spectrum.At for example Li 2S-P 2S 5Under the situation of the sulfide solid electrolyte material of material, S 3P-S-PS 3The peak of unit appears at 402cm usually -1The place.Therefore, preferably, such peak may not be detected.PS 4The peak of unit appears at 417cm usually -1The place.In this embodiment, preferably, at 402cm -1The intensity I at place 402Can be less than at 417cm -1The intensity I at place 417More specifically, intensity I 402Can preferably be not more than intensity I 41770%, more preferably no more than 50%, and more preferably no more than 35%.Remove Li 2S-P 2S 5Outside sulfide solid electrolyte material do not contain or be substantially free of crosslinked sulphur and can have the unit of crosslinked sulphur and confirm through identification through the peak of measuring these unit.
In this embodiment, preferably, Li 2The summation of S and bond fission compound is with respect to Li 2The sulfide of S, the 14th family or the 15th family's element adds that the ratio of the summation of bond fission compound can have the Li that equals or be not less than acquisition ortho acid composition 2The value of the ratio of S, this is because can obtain to be substantially free of the sulfide solid electrolyte material of crosslinked sulphur in this case more reliably.The sulfide of the 14th family or the 15th family's element is P therein 2S 5Situation under, for example, obtain the Li that ortho acid is formed 2The ratio of S is 75%, as stated.Therefore, based on mole meter, Li 2S and bond fission compound (Li for example 2O) summation is with respect to Li 2S, P 2S 5With bond fission compound (Li for example 2The ratio of summation O) can preferably be not less than 75%, more preferably is not less than 76%, and is not less than 77% especially.Based on mole meter, Li 2S and bond fission compound (Li for example 2The ratio of summation O) can preferably be not more than 95%, more preferably no more than 90%, and is not more than 85% especially.This is because under the situation of bond fission compound insulation, the Li ionic conductivity of gained sulfide solid electrolyte material can become relatively bigger along with the ratio of bond fission compound and reduce.
If the sulfide of the 14th family or the 15th family's element is GeS 2, for example, obtain the Li that ortho acid is formed 2The ratio of S is 66.7%, as stated.Therefore, based on mole meter, Li 2S and bond fission compound (Li for example 2O) summation is with respect to Li 2S, GeS 2With bond fission compound (Li for example 2The ratio of summation O) can preferably be not less than 66.7%, more preferably is not less than 67%, and is not less than 68% especially, because can obtain to be substantially free of the sulfide solid electrolyte material of crosslinked sulphur more reliably in this case.Based on mole meter, Li 2S and bond fission compound (Li for example 2The ratio of summation O) can preferably be not more than 95%, more preferably no more than 90%, and is not more than 85% especially.This is because under the situation of bond fission compound insulation, the Li ionic conductivity of gained sulfide solid electrolyte material can become relatively bigger along with the ratio of bond fission compound and reduce.If the sulfide of the 14th family or the 15th family's element is SiS 2, for example, obtain the Li that ortho acid is formed 2The ratio of S is 66.7%.Therefore, Li 2S and bond fission compound (Li for example 2The preferred proportion of summation O) with for GeS 2Identical.
When using Li 2O is during as the bond fission compound, and especially, the Li ionic conductivity of gained sulfide solid electrolyte material can be through regulating Li 2The addition of O increases, and this is because at Li 2Li element among the O can help to improve the Li ionic conductivity.Here, I AFinger is at Li 2S and Li 2The summation of O is with respect to Li 2The sulfide and the Li of S, the 14th family or the 15th family's element 2The ratio of the summation of O is for obtaining the Li that ortho acid is formed 2The Li ionic conductivity of sulfide electrolyte under the situation of the ratio of S.In this embodiment, preferably, Li 2S and Li 2The summation of O is with respect to Li 2The sulfide and the Li of S, the 14th family or the 15th family's element 2The ratio of the summation of O can be set at and obtain to have the I of ratio AThe ratio of the sulfide solid electrolyte material of big Li ionic conductivity.Li 2S and Li 2The lower limit of the summation of O is to surpass to obtain the Li that ortho acid is formed 2The value of the ratio of S.Li 2S and Li 2The upper limit of the summation of O can be through appropriate experiment decision.In this case, obtain to have Li usually 2The sulfide solid electrolyte material of O phase.
Next will explain the second vitrifying process according to this embodiment.The second vitrifying process of this embodiment be make the above-mentioned composition that contains intermediate decrystallized with the process of eliminating crosslinked sulphur.The instance of the second vitrifying process comprises for example mechanical lapping and melt quenching.Preferably, the second vitrifying process can be the mechanical lapping in the aforementioned process, and this is because mechanical lapping can be carried out at normal temperatures and allow to make manufacture process to oversimplify.
Concrete restriction is not done in mechanical lapping, as long as will contain the composition mixing of intermediate and give its mechanical energy simultaneously.Embodiment comprises for example ball milling, turbine mill, machinery fusion, mill.Preferably, mechanical lapping can relate to ball milling, relates to planetary type ball-milling especially, and this is because can obtain the sulfide solid electrolyte material of expectation in this case with good efficiency.
The mechanical lapping condition enactment is to be used to allow the sulfide solid electrolyte material that obtains to expect.If make sulfide solid electrolyte material, for example, will contain in the composition and abrading-ball tank filling of intermediate, and grind preset time with predetermined rotating speed through planetary type ball-milling.Usually, bigger rotating speed changes into sulfide solid electrolyte material generating rate faster.Equally, the processing time is long more, and the conversion ratio that the composition that then contains intermediate changes into sulfide solid electrolyte material becomes high more.Speed setting in planetary type ball-milling is for example 200rpm to 500rpm.In this scope, preferably, rotating speed can be 250rpm to 400rpm.Processing time during planetary type ball-milling for example is 1 hour to 100 hours.In this scope, preferably, the processing time can be 1 hour to 50 hours.
This embodiment allows to provide sulfide solid electrolyte material, it is characterized in that obtaining through the above-mentioned first vitrifying process and the second vitrifying process.
Next explain sulfide solid electrolyte material based on this embodiment.Sulfide solid electrolyte material according to this embodiment comprises Li, the 14th family or the 15th family's element, O and S, is substantially free of crosslinked sulphur, and Li 2The content of S is not more than 1 mole of %.
In this embodiment, Li 2The content of S is low, therefore can obtain to produce the sulfide solid electrolyte material of very a small amount of hydrogen sulfide.
Sulfide solid electrolyte material according to this embodiment has wherein its Li 2S content is not more than the characteristic of 1 mole of %, as stated.Preferably, Li 2S content can be worth less than this.Particularly, Li 2S content can preferably be not more than 0.9 mole of %, and is not more than 0.8 mole of % especially.Li 2S content can calculate based on XPS result.Particularly, measure S 2pXPS spectrum, and can quantize Li through separating the peak obtained 2S content.Li 2The S peak is usually at about 160eV to 162eV (2p1/2: 161.5eV, 2p3/2: 160.3eV) locate to detect.Therefore, Li 2S content can recently calculate based on surface area at the peak after separating.The peak separation condition can relate to for example surface area ratio S 2p1/2: S 2p3/2=1: 2, and offset spacers is 1.3eV.For the match peak, can select for example three kinds of components, i.e. Li 2The sulfide solid electrolyte material that S, ortho acid form (Li for example 3PS 4) and unconventional component.
Li 2S content also can calculate based on the test of the hydrogen sulfide of measuring scheduled volume.Particularly; Weighing 100mg sulfide solid electrolyte material in inert gas atmosphere; And place 1755 milliliters of driers (air atmosphere, 25 ℃ of temperature, humidity 50%) of sealing; Can utilize hydrogen sulfide sensor (GX-2009, Riken KeiKi makes) to measure the generation of hydrogen sulfide thus.Then, can calculate Li based on the maximum (milliliter/gram) of the measuring amount of generation hydrogen sulfide 2S content.
The sulfide solid electrolyte material of this embodiment is characterised in that and is substantially free of crosslinked sulphur.The implication of characteristic " is substantially free of crosslinked sulphur " indication identical with described in above-mentioned " A. makes the method for sulfide solid electrolyte material ".
Sulfide solid electrolyte material according to this embodiment comprises Li, the 14th family or the 15th family's element, O and S.The 14th family or the 15th family's element are not done concrete restriction.Preferably, the 14th family or the 15th family's element can be for example P, Si or Ge, particularly P.The sulfide solid electrolyte material of this embodiment is nature of glass sulfide solid electrolyte material normally.Preferably, the sulfide solid electrolyte material of this embodiment can pass through Li 2The sulfide of S, the 14th family or the 15th family's element and the vitrifying of bond fission compound obtain.The characteristic of the sulfide of the 14th family or the 15th family's element and bond fission compound is as described in above-mentioned the method for sulfide solid electrolyte material " A. make ".Preferably, the sulfide solid electrolyte material according to this embodiment can pass through Li especially 2S, P 2S 5And Li 2The vitrifying of O obtains, and this is because of the sulfide solid electrolyte material that can obtain in this case to produce very small amount of hydrogen sulfide and have good Li ionic conductivity.
Preferably, the sulfide solid electrolyte material according to this embodiment can have Li 2The O phase, this is because can obtain the sulfide solid electrolyte material of also better Li ionic conductivity in this case.Characteristic " has Li 2The O phase " can be for example measure and confirm based on X-ray diffraction (XRD).
Preferably, the sulfide solid electrolyte material according to this embodiment can have high Li ion conductivity value.Ionic conductivity at room temperature can be preferably and for example be not less than 10 -5S/cm more preferably is not less than 10 -4S/cm.Sulfide solid electrolyte material according to this embodiment is generally pulverulence, and its average-size is for example 0.1 μ m to 50 μ m.The purposes of sulfide solid electrolyte material comprises for example lithium battery.
Next will explain lithium battery according to this embodiment.Lithium battery according to this embodiment is to have following lithium battery: the active positive electrode material layer that comprises active positive electrode material; The negative electrode active material layer that comprises negative electrode active material; And the dielectric substrate that between active positive electrode material layer and negative electrode active material layer, forms; Wherein comprise one of at least above-mentioned sulfide solid electrolyte material in active positive electrode material layer, negative electrode active material layer and the dielectric substrate.
This embodiment allows through using above-mentioned sulfide solid electrolyte material to obtain to produce the lithium battery of very small amount of hydrogen sulfide.
Fig. 3 is the schematic cross section that illustrates according to an instance of the generating element in the lithium battery of this embodiment.Has the active positive electrode material layer 1 that comprises active positive electrode material at the generating element shown in Fig. 3 10; The negative electrode active material layer 2 that comprises negative electrode active material; And the dielectric substrate 3 that between active positive electrode material layer 1 and negative electrode active material layer 2, forms.As a notable feature of this embodiment, comprise one of at least above-mentioned sulfide solid electrolyte material in active positive electrode material layer 1, negative electrode active material layer 2 and the dielectric substrate 3.Next will explain multiple structure according to the lithium battery of this embodiment.
At first will explain the dielectric substrate of this embodiment.The dielectric substrate of this embodiment is the layer that between active positive electrode material layer and negative electrode active material layer, forms.Dielectric substrate is not done concrete restriction, as long as it can conduct the Li ion, but preferably, dielectric substrate can be the solid electrolyte layer of solid electrolyte material, and this is because can obtain the lithium battery (all-solid-state battery) of high safety in this case.In this embodiment, preferably, solid electrolyte layer can comprise above-mentioned sulfide solid electrolyte material.The ratio of the sulfide solid electrolyte material in solid electrolyte layer can be for example 10 volume % to 100 volume %, and preferably can be 50 volume % to 100 volume % in this scope.In this embodiment, especially, solid electrolyte layer can preferably only have sulfide solid electrolyte material, and this is because can obtain to produce the lithium battery of a small amount of hydrogen sulfide in this case.The thickness of solid electrolyte layer can be for example 0.1 μ m to 1000 μ m, and can be preferably 0.1 μ m to 300 μ m in this scope.The method that forms solid electrolyte layer can relate to the for example pressing mold of solid electrolyte material.
Dielectric substrate in this embodiment can be for having the layer of electrolyte solution.Can obtain high output lithium battery through using electrolyte solution.In this case, usually, comprise one of at least above-mentioned sulfide solid electrolyte material in active positive electrode material layer and the negative electrode active material layer.Electrolyte solution comprises lithium salts and organic solvent (nonaqueous solvents) usually.The instance of lithium salts comprises for example inorganic lithium salt such as LiPF 6, LiBF 4, LiClO 4Or LiAsF 6With organic lithium salt such as LiCF 3SO 3, LiN (CF 3SO 2) 2, LiN (C 2F 5SO 2) 2Or LiC (CF 3SO 2) 3The instance of organic solvent comprises for example ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC) or butylene carbonate.
Next will explain the active positive electrode material layer of this embodiment.The active positive electrode material layer of this embodiment is to comprise active positive electrode material at least and under maybe the situation of needs, also comprise to be selected from solid electrolyte material, to give the material of conductivity and at least a layer in the adhesive.In this embodiment, preferably, the solid electrolyte material in the active positive electrode material layer can be in particular above-mentioned sulfide solid electrolyte material, because can obtain to produce the lithium battery of very small amount of hydrogen sulfide in this case.The ratio of sulfide solid electrolyte material in the active positive electrode material layer changes according to the type of lithium battery; But can preferably drop in the scope of 0.1 volume % to 80 volume %; And further; In the scope of 1 volume % to 60 volume %, and be 10 volume % to 50 volume % especially.The instance of active positive electrode material comprises for example LiCoO 2, LiMnO 2, Li 2NiMn 3O 8, LiVO 2, LiCrO 2, LiFePO 4, LiCoPO 4, LiNiO 2And LiNi 1/3Co 1/3Mn 1/3O 2
Active positive electrode material layer in this embodiment can also comprise the material of giving conductivity.The conductivity of active positive electrode material layer can strengthen through the material that conductivity is given in interpolation.The instance of giving the material of conductivity comprises for example acetylene black, Ketjen black (Ketjen blakc), carbon fiber etc.The active positive electrode material layer can comprise binding agent.The instance of types of binder comprises for example fluorine-containing binding agent.Preferably, the thickness of active positive electrode material layer can be for example 0.1 μ m to 1000 μ m.
Next will explain the negative electrode active material layer of this embodiment.The negative electrode active material layer of this embodiment is to comprise negative electrode active material at least and under maybe the situation of needs, also comprise to be selected from solid electrolyte material, to give the material of conductivity and at least a layer in the binding agent.In this embodiment, preferably, the solid electrolyte material in the negative electrode active material layer can be in particular above-mentioned sulfide solid electrolyte material, and this is because can obtain to produce the lithium battery of very small amount of hydrogen sulfide in this case.The ratio of sulfide solid electrolyte material in the negative electrode active material layer changes according to the type of lithium battery; But can preferably drop in the scope of 0.1 volume % to 80 volume %; And further; In the scope of 1 volume % to 60 volume % in this scope, and be 10 volume % to 50 volume % especially.Other instance of negative electrode active material comprises for example metal active material and carbon active material.The instance of metal active material comprises for example In, Al, Si and Sn.The instance of carbon active material comprises mesoporous carbon microballon (MCMB) for example, height-oriented pyrolytic graphite (HOPG), hard carbon and soft carbon.The material of giving conductivity that in the negative electrode active material layer, uses and binding agent are identical with in above-mentioned active positive electrode material layer those.Preferably, the thickness of negative electrode active material layer can be for example 0.1 μ m to 1000 μ m.
Lithium battery according to this embodiment has above-mentioned active positive electrode material layer, dielectric substrate and negative electrode active material layer at least.Usually, lithium battery also has the positive electrode current collector of collecting the electric current in the active positive electrode material layer and the negative electrode current collector of collecting the electric current in the negative electrode active material layer.The instance of the material of positive electrode current collector comprises for example stainless steel (SUS), aluminium, nickel, iron, titanium and carbon, and can be preferably SUS, and the SUS in the aforementioned substances more preferably.The instance of the material of negative electrode current collector comprises for example SUS, copper, nickel or carbon, and can be preferably the SUS in the aforementioned substances.Preferably, the thickness of positive electrode current collector and negative electrode current collector, shape etc. can be come appropriate the selection according to the purposes of for example lithium battery.The battery case that in this embodiment, uses can be the battery case that in common lithium battery, uses.The instance of battery case comprises the battery case of for example being processed by SUS.Lithium battery according to this embodiment is under the situation of all-solid-state battery therein, and generating element can be formed in the dead ring.
Lithium battery based on this embodiment can be one-shot battery or secondary cell.Preferably, lithium battery can be a secondary cell, and this is because in this case, and battery can recharge and discharge, therefore can be as for example on-vehicle battery.The instance of the shape of the lithium battery of this embodiment comprises for example coin shapes, range upon range of shape, tubulose, square configuration etc.
Manufacturing is not done concrete restriction based on the method for the manufacturing lithium battery of this embodiment, as long as can obtain above-mentioned lithium battery, and can use and the identical method of method that is used to make conventional lithium battery.For example; Be under the situation of all-solid-state battery according to this embodiment lithium battery; An instance of its manufacturing approach can comprise that the order compacting constitutes the material of active positive electrode material layer, constitutes the material of solid electrolyte layer and the material of formation negative electrode active material layer, to produce generating element thus.Then generating element is loaded in the battery case, and battery case is curled.This embodiment also allows to provide and is characterised in that active positive electrode material layer, negative electrode active material layer and the solid electrolyte layer that comprises above-mentioned sulfide solid electrolyte material.
The invention is not restricted to above-mentioned embodiment.Previous embodiments only is an illustrative in nature.Therefore, the scope of embodiment contain have with according to the substantially the same characteristic of the characteristic of the embodiment and the technical conceive of in claim, setting forth and produce and any structure of the essentially identical effect of this technical conceive.
Next explain specific embodiment of the present invention.
Lithium sulfide (Li is used in (embodiment 1) 2S) and phosphoric sulfide (P 2S 5) as starting material.In the glove box in being in argon atmospher with Li 2S: P 2S 5The powder of=70: 30 the aforementioned material of molar ratio weighing, and in agate mortar, mix, to produce 1g starting material composition.Next, the 1g starting material composition that is obtained is placed 45ml zirconia jar, to the zirconia ball of wherein further packing into (Ф 10mm, 10 balls), and complete hermetically sealed can.With the canned planetary ball mill that is fitted on, and carried out mechanical lapping 20 hours, to obtain the intermediate (70Li of sulfide solid electrolyte material with the table top rotating speed of 370rpm 2S30P 2S 5Glass).Next, add lithia (Li to the intermediate that is obtained 2O) to forming xLi 2O (1-x) (70Li 2S30P 2S 5) in the mol ratio of x=0.17.Make whole gains stand mechanical lapping in the same manner as described above 40 hours, to obtain sulfide solid electrolyte material (17Li 2O58Li 2S25P 2S 5).
(embodiment 2) with embodiment 1 in identical mode obtain sulfide solid electrolyte material (20Li 2O56Li 2S24P 2S 5Glass), still add lithia (Li herein 2O) to forming xLi 2O (1-x) (70Li 2S30P 2S 5) in the mol ratio of x=0.20.
(embodiment 3) with embodiment 1 in identical mode obtain sulfide solid electrolyte material (25Li 2O52.5Li 2S22.5P 2S 5Glass), still add lithia (Li herein 2O) to forming xLi 2O (1-x) (70Li 2S30P 2S 5) in the mol ratio of x=0.25.
(Comparative Examples 1) used lithium sulfide (Li 2S), phosphoric sulfide (P 2S 5) and lithia (Li 2O) as starting material.The powder of the aforementioned material of weighing is to forming xLi in the glove box in being in argon atmospher 2O (1-x) (70Li 2S30P 2S 5) in the mol ratio of x=0.17, and in agate mortar, mix, to produce 1g starting material composition.Next, the 1g starting material composition that is obtained is placed 45ml zirconia jar, to the zirconia ball of wherein further packing into (Ф 10mm, 10 balls), and complete hermetically sealed can.With the canned planetary ball mill that is fitted on, and carried out mechanical lapping 40 hours, to obtain the intermediate (17Li of sulfide solid electrolyte material with the table top rotating speed of 370rpm 2O58Li 2S25P 2S 5Glass).
(Comparative Examples 2) with Comparative Examples 1 in identical mode obtain sulfide solid electrolyte material (20Li 2O56Li 2S24P 2S 5Glass), still be revised as herein to forming xLi 2O (1-x) (70Li 2S30P 2S 5) in the mol ratio of x=0.20.
(Comparative Examples 3) with Comparative Examples 1 in identical mode obtain sulfide solid electrolyte material (25Li 2O52.5Li 2S22.5P 2S 5Glass), still change into herein at composition xLi 2O (1-x) (70Li 2S30P 2S 5) in x=0.25 thick you the ratio.
(Comparative Examples 4) used lithium sulfide (Li 2S) and phosphoric sulfide (P 2S 5) as starting material.In the glove box in being in argon atmospher with Li 2S: P 2S 5The powder of=75: 25 the aforementioned material of molar ratio weighing, and in agate mortar, mix, to produce 1g starting material composition.Next, the 1g starting material composition that is obtained is placed 45ml zirconia jar, to the zirconia ball of wherein further packing into (Ф 10mm, 10 balls), and complete hermetically sealed can.With the canned planetary ball mill that is fitted on, and carried out mechanical lapping 40 hours, to obtain sulfide solid electrolyte material (75Li with the table top rotating speed of 370rpm 2S25P 2S 5Glass).
(measurement of the amount of the hydrogen sulfide that is produced) be utilized among the embodiment 1-3 with Comparative Examples 1-4 in the sulfide solid electrolyte material that obtains measure the hydrogen sulfide generation.The generation of hydrogen sulfide is measured as follows.Particularly; The powder of weighing 100mg sulfide solid electrolyte material in inert atmosphere; And be placed on the 1755cc drier (air atmosphere, 25 ℃ of temperature, humidity 50%) of sealing; After this utilize hydrogen sulfide sensor (GX-2009 is made by Riken Keiki) to measure the generation of hydrogen sulfide.The result is shown in the Figure 4 and 5.In embodiment 1-3, the generation of hydrogen sulfide is not more than the detectable limit of transducer (0.009cc/g), as shown in Fig. 4.At the 75Li shown in Fig. 4 2S25P 2S 5The result be those of Comparative Examples 4, describe the latter and be for as reference.In contrast to this, in Comparative Examples 1-4, observed the generation of hydrogen sulfide, as shown in fig. 5.
Be utilized in the sulfide solid electrolyte material that obtains among embodiment 1-3 and the Comparative Examples 1-3 and carry out the X-ray diffraction measurement.The result is shown in Fig. 6 and 7.As shown in Figure 6, Li in embodiment 1 2O and Li 2The summation of S is 75 moles of %, does not therefore detect Li 2The O peak.In contrast to this, in embodiment 2 and 3, Li 2O and Li 2The summation of S surpasses 75 moles of %, therefore detects Li 2The O peak.As shown in Figure 7, Li in Comparative Examples 1 2O and Li 2The summation of S is 75 moles of %, does not therefore detect Li 2The O peak.In contrast to this, in Comparative Examples 2 and Comparative Examples 3, Li 2O and Li 2The summation of S surpasses 75 moles of %, therefore detects Li 2The O peak.Li in embodiment 2 2The O peak is than the Li in Comparative Examples 2 2The O peak is point a little more.Equally, the Li in embodiment 3 2The O peak is than the Li in Comparative Examples 3 2The O peak is point a little more.Suppose that this is owing to Li in the intermediate 2S and Li 2Highly effective reaction between the O, this is because the reaction of vitrifying in an embodiment is divided into two stages.
The sulfide solid electrolyte material that in Comparative Examples 4, obtains is carried out X-ray diffraction to be measured.The result is shown in Fig. 8.As shown in Figure 8, do not observe Li through X-ray diffraction 2The S peak.Yet the result of Fig. 5 is illustrated in the amount of the hydrogen sulfide that produces in the Comparative Examples 4 greater than the amount in other Comparative Examples.This means that existence measures undetectable Li with X-ray diffraction 2The height possibility of S.
Be utilized in the sulfide solid electrolyte material that obtains among embodiment 1-3 and the Comparative Examples 1-4 and carry out the measurement of Li ionic conductivity.The Li ionic conductivity is measured as follows.The powder of sulfide solid electrolyte material is processed pill, and at room temperature measure the Li ionic conductivity according to the AC impedance method.The result is shown in Fig. 9.As shown in Figure 9, the Li ionic conductivity in embodiment 1-3 is higher than the Li ionic conductivity in Comparative Examples 1-3.The Li ionic conductivity is at embodiment 2 (Li 2O=20 mole %) shows 1.6 * 10 near -4The maximum of S/cm.In contrast to this, the Li ionic conductivity in Comparative Examples 2 is 1.2 * 10 -4S/cm.Therefore, embodiment 2 shows the Li ionic conductivity of about 1.3 times Comparative Examples 2.
Be utilized in the sulfide solid electrolyte material that obtains among the Comparative Examples 1-4 and carry out the x-ray photoelectron spectroscopy measurement.The result provides in Figure 10-13.Shown in Figure 10-13, measure undetectable Li through X-ray diffraction 2S detects through XPS.Li according to above-mentioned peak separation condition 2The S content measurement shows, the Li in Comparative Examples 1 2S content is 3 moles of %, the Li in Comparative Examples 2 2S content is 2 moles of %, the Li in Comparative Examples 3 2S content is 1.5 moles of %, and the Li in Comparative Examples 4 2S content is 4.7 moles of %.
Though preceding text have shown embodiments more of the present invention; But be to be understood that; The invention is not restricted to the details of shown embodiment, but can be presented as multiple variation, modification or improvement project that those of ordinary skills can expect, and do not depart from the scope of the present invention.

Claims (16)

1. method of making sulfide solid electrolyte material is characterized in that comprising:
In the first vitrifying process through the vitrifying of starting material composition being formed have crosslinked sulphur but do not have Li 2The intermediate of S, said starting material composition passes through Li 2The sulfide of S and the 14th family or the 15th family's element is mixed into and makes Li 2S is with respect to said Li 2The ratio of the summation of the said sulfide of S and the 14th family or the 15th family's element obtains ortho acid less than said sulfide solid electrolyte material and forms required Li 2The ratio of S and obtaining; With
Through making the composition vitrifying that contains intermediate eliminate said crosslinked sulphur, the said composition that contains intermediate makes the bond fission compound and the said intermediate of the bond fission of said crosslinked sulphur obtain through mixing in the second vitrifying process.
2. manufacturing approach according to claim 1, the said ratio that wherein said bond fission compound mixes with said intermediate are substantially free of the ratio of the sulfide solid electrolyte material of crosslinked sulphur for acquisition.
3. manufacturing approach according to claim 1 and 2, wherein said bond fission compound is Li 2O.
4. according to each described manufacturing approach in the claim 1 to 3, wherein:
The said sulfide of the 14th family or the 15th family's element is P 2S 5And
In said starting material composition, in mole, said Li 2S is with respect to said Li 2S and said P 2S 5The ratio of summation less than 75%.
5. manufacturing approach according to claim 4, wherein in the said composition that contains intermediate, in mole, said Li 2S and said Li 2The summation of O is with respect to said Li 2S, said P 2S 5With said Li 2The ratio of the summation of O is not less than 75%.
6. according to each described manufacturing approach in the claim 1 to 3, wherein the said sulfide of the 14th family or the 15th family's element is GeS 2And in said starting material composition, in mole, said Li 2S is with respect to said Li 2S and said GeS 2The ratio of summation less than 66.7%.
7. manufacturing approach according to claim 6, wherein in the said composition that contains intermediate, in mole, said Li 2S and said Li 2The summation of O is with respect to said Li 2S, said GeS 2With said Li 2The ratio of the summation of O is not less than 66.7%.
8. according to each described manufacturing approach in the claim 1 to 3, wherein:
The said sulfide of the 14th family or the 15th family's element is SiS 2And
In said starting material composition, in mole, said Li 2S is with respect to said Li 2S and said SiS 2The ratio of summation less than 66.7%.
9. manufacturing approach according to claim 8, wherein in the said composition that contains intermediate, in mole, said Li 2S and said Li 2The summation of O is with respect to said Li 2S, said SiS 2With said Li 2The ratio of the summation of O is not less than 66.7%.
10. according to each described manufacturing approach in the claim 1 to 9, the wherein said first vitrifying process is mechanical lapping.
11. according to each described manufacturing approach in the claim 1 to 10, wherein: the said second vitrifying process is mechanical lapping.
12. a sulfide solid electrolyte material is characterized in that comprising: Li, the 14th family or the 15th family's element, O and S;
Said material is substantially free of crosslinked sulphur, wherein
Li 2The content of S is not more than 1 mole of %.
13. sulfide solid electrolyte material according to claim 12, wherein said the 14th family or the 15th family's element are P.
14. sulfide solid electrolyte material according to claim 13, it is through making Li 2S, P 2S 5And Li 2The O vitrifying is made.
15. according to each described sulfide solid electrolyte material in the claim 12 to 14, wherein said Li 2O forms phase.
16. a lithium battery is characterized in that comprising:
The active positive electrode material layer that comprises active positive electrode material;
The negative electrode active material layer that comprises negative electrode active material; With
Be formed on the dielectric substrate between said active positive electrode material layer and the said negative electrode active material layer,
Comprising one of at least in said active positive electrode material layer, said negative electrode active material layer and the said dielectric substrate according to each described sulfide solid electrolyte material in the claim 12 to 15.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103560267A (en) * 2013-11-01 2014-02-05 国家电网公司 Electrolyte material for all solid-state lithium secondary battery, preparation method for electrolyte material and all solid-state lithium secondary battery
CN106257731A (en) * 2015-06-16 2016-12-28 现代自动车株式会社 Prepare the method for lithium ion conducting sulfide and the lithium ion conducting sulfide of preparation
CN110451781A (en) * 2019-07-01 2019-11-15 中国科学院上海光学精密机械研究所 A kind of high ionic conductivity mixes chlorine molybdophosphate glass and preparation method thereof
CN113039616A (en) * 2018-12-28 2021-06-25 松下知识产权经营株式会社 Solid electrolyte material and battery using the same

Families Citing this family (113)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5141675B2 (en) 2009-12-16 2013-02-13 トヨタ自動車株式会社 Method for producing sulfide solid electrolyte material, sulfide solid electrolyte material, and lithium battery
CN103003890B (en) 2010-07-22 2016-01-20 丰田自动车株式会社 The manufacture method of sulfide solid electrolyte glass, sulfide solid electrolyte glass and lithium solid state battery
US9543622B2 (en) * 2011-07-26 2017-01-10 Toyota Jidosha Kabushiki Kaisha Lithium solid state secondary battery system
JP5806621B2 (en) * 2012-01-31 2015-11-10 出光興産株式会社 Solid electrolyte glass and lithium ion battery using the same
JP6139078B2 (en) * 2012-09-03 2017-05-31 古河機械金属株式会社 Solid electrolyte material for lithium ion battery, solid electrolyte for lithium ion battery, lithium ion battery, and method for producing solid electrolyte material for lithium ion battery
JP2014091664A (en) * 2012-11-06 2014-05-19 Idemitsu Kosan Co Ltd Solid electrolyte glass particles and lithium ion battery
KR101352791B1 (en) * 2012-12-18 2014-01-16 국립대학법인 울산과학기술대학교 산학협력단 Structure for ionic conductive way of electrolyte membrane in lithium ion secondary battery
JP5561383B2 (en) * 2013-01-11 2014-07-30 トヨタ自動車株式会社 Sulfide solid electrolyte material, battery, and method for producing sulfide solid electrolyte material
JP6056955B2 (en) * 2013-03-05 2017-01-11 日本電気株式会社 Lithium secondary battery
JP6062308B2 (en) * 2013-04-09 2017-01-18 古河機械金属株式会社 Solid electrolyte material for lithium ion battery, solid electrolyte for lithium ion battery, lithium ion battery, and method for producing solid electrolyte material for lithium ion battery
JP5720753B2 (en) * 2013-10-02 2015-05-20 トヨタ自動車株式会社 Sulfide solid electrolyte material, battery, and method for producing sulfide solid electrolyte material
US9853323B2 (en) 2013-10-31 2017-12-26 Samsung Electronics Co., Ltd. Positive electrode for lithium-ion secondary battery, and lithium-ion secondary battery
JP6288716B2 (en) 2014-06-25 2018-03-07 国立大学法人東京工業大学 Method for producing sulfide solid electrolyte material
KR101671219B1 (en) 2015-05-04 2016-11-01 창원대학교 산학협력단 Method for preparing All-Solid-State Lithium-Sulfur batteries and Lithium-Sulfur batteries prepared thereby
JP6380263B2 (en) * 2015-06-29 2018-08-29 トヨタ自動車株式会社 Method for producing sulfide solid electrolyte
JP6877084B2 (en) 2015-07-31 2021-05-26 国立大学法人東京工業大学 α-Lithium solid electrolyte
JP6780000B2 (en) * 2015-12-17 2020-11-04 トヨタ・モーター・ヨーロッパＴｏｙｏｔａ Ｍｏｔｏｒ Ｅｕｒｏｐｅ All-solid-state battery using a sodium ion-inserted cathode with a Li / Na exchange layer
JP6531674B2 (en) 2016-02-26 2019-06-19 トヨタ自動車株式会社 Sulfide solid electrolyte material, lithium solid battery and method for producing sulfide solid electrolyte material
KR101862784B1 (en) 2016-04-27 2018-05-31 한국과학기술연구원 A method of producing a lithium ion conductive sulfide by independent mixing sulfur compound with simple substance
CN107394120B (en) 2016-05-16 2022-03-29 松下知识产权经营株式会社 Sulfide solid electrolyte material, positive electrode material, and battery
CN114937812A (en) 2016-08-04 2022-08-23 松下知识产权经营株式会社 Solid electrolyte material and battery
CN106450440B (en) * 2016-09-13 2020-08-04 清华大学 All-solid-state lithium ion battery, solid electrolyte compound and preparation method
KR102417506B1 (en) 2016-11-16 2022-07-05 현대자동차주식회사 Solid electrolyte derived from single substance and preparing method thereof
US11271245B2 (en) 2017-03-22 2022-03-08 Mitsubishi Gas Chemical Company, Inc. Production method for solid electrolyte having Li3PS4
JP7209169B2 (en) 2017-04-27 2023-01-20 パナソニックＩｐマネジメント株式会社 solid electrolyte materials, electrode materials, positive electrodes, and batteries
KR102004245B1 (en) 2017-11-16 2019-07-26 단국대학교 천안캠퍼스 산학협력단 Preparing method of norathyriol using eco-friendly C-deglycosylation
KR102507008B1 (en) 2017-12-20 2023-03-06 현대자동차주식회사 A sulfide-based solid electrolyte for all-solid battery having a crystal structure of argyrodite derived from single substance and preparing method thereof
KR102484902B1 (en) 2017-12-27 2023-01-04 현대자동차주식회사 All solid battery
WO2019135346A1 (en) 2018-01-05 2019-07-11 パナソニックＩｐマネジメント株式会社 Positive electrode material and battery
CN111295719B (en) 2018-01-05 2022-03-29 松下知识产权经营株式会社 Solid electrolyte material and battery
EP3736834A4 (en) 2018-01-05 2021-03-10 Panasonic Intellectual Property Management Co., Ltd. Solid electrolyte material, and battery
JP7253707B2 (en) 2018-01-05 2023-04-07 パナソニックＩｐマネジメント株式会社 solid electrolyte material and battery
CN111279430B (en) 2018-01-05 2022-01-04 松下知识产权经营株式会社 Solid electrolyte material and battery
CN111295789B (en) 2018-01-05 2024-07-19 松下知识产权经营株式会社 Solid electrolyte material and battery
EP3736829A4 (en) 2018-01-05 2021-03-10 Panasonic Intellectual Property Management Co., Ltd. Solid electrolyte material and battery
CN111295721B (en) 2018-01-05 2022-04-26 松下知识产权经营株式会社 Solid electrolyte material and battery
CN111316378B (en) 2018-01-05 2021-09-28 松下知识产权经营株式会社 Solid electrolyte material and battery
EP3736822A4 (en) 2018-01-05 2021-03-10 Panasonic Intellectual Property Management Co., Ltd. Solid electrolyte material and battery
CN111492524B (en) 2018-01-05 2024-07-12 松下知识产权经营株式会社 Solid electrolyte material and battery
CN111279431B (en) 2018-01-05 2022-03-25 松下知识产权经营株式会社 Solid electrolyte material and battery
WO2019135341A1 (en) 2018-01-05 2019-07-11 パナソニックＩｐマネジメント株式会社 Solid electrolyte material, and battery
CN111480258B (en) 2018-01-05 2024-05-24 松下知识产权经营株式会社 Battery cell
CN111557058B (en) 2018-01-05 2023-09-01 松下知识产权经营株式会社 Solid electrolyte material and battery
WO2019135348A1 (en) 2018-01-05 2019-07-11 パナソニックＩｐマネジメント株式会社 Solid electrolyte material and battery
EP3745422A4 (en) 2018-01-26 2021-03-10 Panasonic Intellectual Property Management Co., Ltd. Solid electrolyte material and battery
EP3745508A4 (en) 2018-01-26 2021-03-17 Panasonic Intellectual Property Management Co., Ltd. Positive electrode material and battery using same
EP3745503A4 (en) 2018-01-26 2021-03-10 Panasonic Intellectual Property Management Co., Ltd. Positive electrode material and battery using same
CN111587508A (en) 2018-01-26 2020-08-25 松下知识产权经营株式会社 Battery with a battery cell
CN111566757B (en) 2018-01-26 2022-08-12 松下知识产权经营株式会社 Solid electrolyte material and battery
KR102139975B1 (en) 2018-08-28 2020-08-03 현대엔지니어링 주식회사 Thermoplastic Elastomer Composition For Reducing Floor Impact Sound And Foamed Articles Therefrom
CN112136184B (en) 2018-10-01 2022-08-12 松下知识产权经营株式会社 Halide solid electrolyte material and battery using the same
EP3863028A4 (en) 2018-10-01 2021-12-08 Panasonic Intellectual Property Management Co., Ltd. Halide solid electrolyte material and battery using same
EP3863027B1 (en) 2018-10-01 2022-06-01 Panasonic Intellectual Property Management Co., Ltd. Halide solid electrolyte material and battery using this
JP7542196B2 (en) * 2018-10-01 2024-08-30 パナソニックＩｐマネジメント株式会社 Halide solid electrolyte material and battery using same
JP2020061305A (en) * 2018-10-11 2020-04-16 古河機械金属株式会社 Phosphorus pentasulfide composition for sulfide-based inorganic solid electrolytic material
WO2020110479A1 (en) 2018-11-29 2020-06-04 パナソニックＩｐマネジメント株式会社 Negative electrode material and battery
JP7429870B2 (en) 2018-11-29 2024-02-09 パナソニックＩｐマネジメント株式会社 Negative electrode materials and batteries
CN112789692B (en) 2018-12-26 2024-01-09 松下知识产权经营株式会社 Solid electrolyte material and battery using the same
WO2020137392A1 (en) 2018-12-26 2020-07-02 パナソニックＩｐマネジメント株式会社 Solid electrolyte material and cell using same
WO2020137154A1 (en) 2018-12-28 2020-07-02 パナソニックＩｐマネジメント株式会社 Solid electrolyte material and battery using same
EP3905272B1 (en) 2018-12-28 2023-01-18 Panasonic Intellectual Property Management Co., Ltd. Solid electrolyte material and battery using same
JP7515114B2 (en) 2018-12-28 2024-07-12 パナソニックＩｐマネジメント株式会社 Solid electrolyte material and battery using same
JP7329776B2 (en) 2018-12-28 2023-08-21 パナソニックＩｐマネジメント株式会社 Solid electrolyte material and battery using the same
WO2020137043A1 (en) 2018-12-28 2020-07-02 パナソニックＩｐマネジメント株式会社 Lithium ion conductive solid electrolyte material, and battery using same
JP7445868B2 (en) 2018-12-28 2024-03-08 パナソニックＩｐマネジメント株式会社 Solid electrolyte materials and batteries using them
JP7432897B2 (en) 2018-12-28 2024-02-19 パナソニックＩｐマネジメント株式会社 Solid electrolyte materials and batteries using them
CN113454735B (en) 2019-02-28 2023-12-08 松下知识产权经营株式会社 Electrolyte material and battery using the same
WO2020188913A1 (en) 2019-03-15 2020-09-24 パナソニックＩｐマネジメント株式会社 Solid electrolyte material and battery using same
CN113474909A (en) 2019-03-15 2021-10-01 松下知识产权经营株式会社 Solid electrolyte material and battery using the same
EP3940816B1 (en) 2019-03-15 2024-05-01 Panasonic Intellectual Property Management Co., Ltd. Solid electrolyte material and battery using same
CN113519084A (en) 2019-03-26 2021-10-19 松下知识产权经营株式会社 Solid electrolyte material and battery using the same
JP7445876B2 (en) 2019-03-26 2024-03-08 パナソニックＩｐマネジメント株式会社 Solid electrolyte materials and batteries using them
EP3995452A4 (en) 2019-07-04 2022-08-31 Panasonic Intellectual Property Management Co., Ltd. Solid electrolyte material and battery using same
JP7478989B2 (en) 2019-07-04 2024-05-08 パナソニックＩｐマネジメント株式会社 Solid electrolyte material and battery using same
EP4044291A4 (en) 2019-10-10 2022-11-09 Panasonic Intellectual Property Management Co., Ltd. Solid electrolyte material and battery using same
JP7565544B2 (en) 2019-10-17 2024-10-11 パナソニックＩｐマネジメント株式会社 Solid electrolyte material and battery using same
CN114945996A (en) 2020-01-29 2022-08-26 松下知识产权经营株式会社 Solid electrolyte material and battery using the same
WO2021152979A1 (en) 2020-01-29 2021-08-05 パナソニックＩｐマネジメント株式会社 Solid electrolyte material and battery using same
EP4106043A4 (en) 2020-02-14 2023-07-19 Panasonic Intellectual Property Management Co., Ltd. Solid electrolyte material and battery using same
JPWO2021161605A1 (en) 2020-02-14 2021-08-19
CN115088111A (en) 2020-02-14 2022-09-20 松下知识产权经营株式会社 Solid electrolyte material and battery using the same
JP7243662B2 (en) * 2020-02-21 2023-03-22 トヨタ自動車株式会社 Method for producing sulfide solid electrolyte
JPWO2021186809A1 (en) 2020-03-18 2021-09-23
JPWO2021186832A1 (en) 2020-03-18 2021-09-23
JPWO2021186845A1 (en) 2020-03-18 2021-09-23
EP4123745A4 (en) 2020-03-18 2023-11-08 Panasonic Intellectual Property Management Co., Ltd. Solid electrolyte material and battery in which same is used
JPWO2021199640A1 (en) 2020-03-31 2021-10-07
EP4131286A4 (en) 2020-03-31 2023-10-04 Panasonic Intellectual Property Management Co., Ltd. Solid electrolyte material and battery using same
JPWO2021199676A1 (en) 2020-03-31 2021-10-07
WO2021199641A1 (en) 2020-03-31 2021-10-07 パナソニックＩｐマネジメント株式会社 Solid electrolyte material and battery using same
EP4131500A4 (en) 2020-03-31 2023-09-27 Panasonic Intellectual Property Management Co., Ltd. Solid electrolyte material and battery using same
WO2021199619A1 (en) 2020-03-31 2021-10-07 パナソニックＩｐマネジメント株式会社 Solid electrolyte material and battery using same
WO2021199677A1 (en) 2020-03-31 2021-10-07 パナソニックＩｐマネジメント株式会社 Solid electrolyte material, battery using same, and method for producing solid electrolyte material
EP4131504A4 (en) 2020-03-31 2023-09-27 Panasonic Intellectual Property Management Co., Ltd. Solid electrolyte material and battery using same
JPWO2021220578A1 (en) 2020-04-30 2021-11-04
CN115398694A (en) 2020-04-30 2022-11-25 松下知识产权经营株式会社 Solid electrolyte material and battery using the same
CN115699390A (en) 2020-06-08 2023-02-03 松下知识产权经营株式会社 Solid electrolyte material and battery using the same
WO2022018990A1 (en) 2020-07-22 2022-01-27 パナソニックＩｐマネジメント株式会社 Solid electrolyte material, and battery using same
WO2022018952A1 (en) 2020-07-22 2022-01-27 パナソニックＩｐマネジメント株式会社 Solid electrolyte material and battery using same
WO2022018946A1 (en) 2020-07-22 2022-01-27 パナソニックＩｐマネジメント株式会社 Solid electrolyte material and battery using same
US11928472B2 (en) 2020-09-26 2024-03-12 Intel Corporation Branch prefetch mechanisms for mitigating frontend branch resteers
WO2022091565A1 (en) 2020-10-28 2022-05-05 パナソニックＩｐマネジメント株式会社 Solid electrolyte material, and battery using same
JPWO2022091566A1 (en) 2020-10-28 2022-05-05
CN112551599B (en) * 2020-12-10 2022-11-11 西安交通大学深圳研究院 Nickel sulfate nanosheet/graphene composite material and preparation method thereof
JPWO2022180980A1 (en) 2021-02-26 2022-09-01
CN116964687A (en) 2021-02-26 2023-10-27 松下知识产权经营株式会社 Solid electrolyte material and battery using the same
CN116888686A (en) 2021-03-02 2023-10-13 松下知识产权经营株式会社 Solid electrolyte material and battery using the same
WO2022185637A1 (en) 2021-03-02 2022-09-09 パナソニックＩｐマネジメント株式会社 Solid electrolyte material and battery using same
CN116868282A (en) 2021-03-02 2023-10-10 松下知识产权经营株式会社 Solid electrolyte material and battery using the same
JPWO2023013391A1 (en) 2021-08-06 2023-02-09
WO2023013306A1 (en) 2021-08-06 2023-02-09 パナソニックＩｐマネジメント株式会社 Solid electrolyte material and battery using same
JPWO2023042567A1 (en) 2021-09-15 2023-03-23
JPWO2023042560A1 (en) 2021-09-15 2023-03-23

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6322929B1 (en) * 1998-02-03 2001-11-27 Matsushita Electric Industrial Co., Ltd. Lithium secondary battery with a high charge-discharge efficiency and a low self-discharging tendency
JP2002109955A (en) * 2000-10-02 2002-04-12 Osaka Prefecture Sulfide crystallized glass, solid electrolyte, and fully solid secondary cell
US6428935B1 (en) * 1998-11-10 2002-08-06 Matsushita Electric Industrial Co., Ltd. Lithium secondary battery
CN1465114A (en) * 2001-02-28 2003-12-31 住友电气工业株式会社 Inorganic solid electrolyte and lithium cell component
JP2004265685A (en) * 2003-02-28 2004-09-24 Idemitsu Petrochem Co Ltd Manufacturing method of lithium ion conductive sulfide glass and glass ceramic and all solid type battery using the glass ceramic

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0670905B2 (en) 1982-10-19 1994-09-07 三洋電機株式会社 Solid electrolyte battery
US4599284A (en) 1985-10-01 1986-07-08 Union Carbide Corporation Vitreous phosphorus oxide-sulfide solid lithium electrolyte
US5217826A (en) * 1990-07-31 1993-06-08 Matsushita Electric Industrial Co., Ltd. Lithium-ion conducting solid electrolyte
JP3151925B2 (en) 1992-05-07 2001-04-03 松下電器産業株式会社 Amorphous lithium ion conductive solid electrolyte and its synthesis method
JP3163741B2 (en) * 1992-05-08 2001-05-08 松下電器産業株式会社 Amorphous lithium ion conductive solid electrolyte and method for producing the same
JP3129018B2 (en) 1993-03-22 2001-01-29 松下電器産業株式会社 Lithium ion conductive solid electrolyte and its synthesis method
JP3528866B2 (en) 1994-06-03 2004-05-24 出光石油化学株式会社 Method for producing lithium sulfide
JP2001328816A (en) * 2000-05-19 2001-11-27 National Institute For Materials Science Cubic lithium-iron chloride crystal, method for producing the same and lithium secondary battery by using the same
JP2003206111A (en) 2002-01-07 2003-07-22 National Institute For Materials Science Lithium thiophosphate compound and lithium phosphate- thiophosphate compound and method for manufacturing those
CN1871177B (en) 2003-10-23 2010-12-22 出光兴产株式会社 Method for purifying lithium sulfide
JP4813767B2 (en) 2004-02-12 2011-11-09 出光興産株式会社 Lithium ion conductive sulfide crystallized glass and method for producing the same
JP4754209B2 (en) 2004-12-16 2011-08-24 日本化学工業株式会社 Method for producing lithium cobalt composite oxide powder
CN101326673B (en) * 2005-12-09 2010-11-17 出光兴产株式会社 Lithium ion conductive sulfide solid electrolyte and all-solid-state lithium battery using same
JP2008078119A (en) 2006-08-25 2008-04-03 Ngk Insulators Ltd Totally solid storage element
JP2009093727A (en) 2007-10-05 2009-04-30 Kayaku Japan Co Ltd Device for preventing hard disk readout
JP4692556B2 (en) 2008-02-12 2011-06-01 トヨタ自動車株式会社 All-solid lithium secondary battery
JP5239375B2 (en) 2008-02-14 2013-07-17 トヨタ自動車株式会社 All-solid battery and method for manufacturing the same
JP2009283344A (en) * 2008-05-23 2009-12-03 Idemitsu Kosan Co Ltd Negative electrode mix for lithium battery, negative electrode for lithium battery, lithium battery, device, and manufacturing method of negative electrode mix for lithium battery
JP5680288B2 (en) 2008-07-07 2015-03-04 トヨタ自動車株式会社 Method for producing sulfide solid electrolyte
CN102160232B (en) 2008-10-03 2014-07-02 丰田自动车株式会社 Process for producing whole solid type lithium battery
JP5141675B2 (en) 2009-12-16 2013-02-13 トヨタ自動車株式会社 Method for producing sulfide solid electrolyte material, sulfide solid electrolyte material, and lithium battery
JP5521899B2 (en) 2010-08-26 2014-06-18 トヨタ自動車株式会社 Sulfide solid electrolyte material and lithium solid state battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6322929B1 (en) * 1998-02-03 2001-11-27 Matsushita Electric Industrial Co., Ltd. Lithium secondary battery with a high charge-discharge efficiency and a low self-discharging tendency
US6428935B1 (en) * 1998-11-10 2002-08-06 Matsushita Electric Industrial Co., Ltd. Lithium secondary battery
JP2002109955A (en) * 2000-10-02 2002-04-12 Osaka Prefecture Sulfide crystallized glass, solid electrolyte, and fully solid secondary cell
CN1465114A (en) * 2001-02-28 2003-12-31 住友电气工业株式会社 Inorganic solid electrolyte and lithium cell component
JP2004265685A (en) * 2003-02-28 2004-09-24 Idemitsu Petrochem Co Ltd Manufacturing method of lithium ion conductive sulfide glass and glass ceramic and all solid type battery using the glass ceramic

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AU2010332402B2 (en) 2013-07-11
US20180269521A1 (en) 2018-09-20
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